EP0221010A1 - Système de photo-initiation pour compositions polymérisables par vote radicalaire - Google Patents

Système de photo-initiation pour compositions polymérisables par vote radicalaire Download PDF

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Publication number
EP0221010A1
EP0221010A1 EP86810416A EP86810416A EP0221010A1 EP 0221010 A1 EP0221010 A1 EP 0221010A1 EP 86810416 A EP86810416 A EP 86810416A EP 86810416 A EP86810416 A EP 86810416A EP 0221010 A1 EP0221010 A1 EP 0221010A1
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EP
European Patent Office
Prior art keywords
alkyl
phenyl
substituted
composition according
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86810416A
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German (de)
English (en)
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EP0221010B1 (fr
Inventor
Leslie R. Gatechair
Gary M. Blumenstein
Peter J. Schirmann
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Novartis AG
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Ciba Geigy AG
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Publication date
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Priority to AT86810416T priority Critical patent/ATE42644T1/de
Publication of EP0221010A1 publication Critical patent/EP0221010A1/fr
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Publication of EP0221010B1 publication Critical patent/EP0221010B1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/04—Chromates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/115—Cationic or anionic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/117—Free radical
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/124—Carbonyl compound containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/126—Halogen compound containing

Definitions

  • the invention relates to photopolymerizable compositions composed of a radically polymerizable material and a combination of two photoinitiators, a process for photopolymerizing such compositions and a process for producing photographic relief images.
  • EP-A-94914 a curable composition of a cationically polymerizable material and an ⁇ -arene metal complex as an initiator. This composition can either be cured directly by heating or the initiator is first activated by radiation and then cured thermally. For complete curing, however, exposure has to take a relatively long time, which is uneconomical. An increase in the sensitivity of the photoinitiator is therefore desirable. It would also be desirable to be able to effect curing by radiation alone without thermal treatment.
  • radical photo hardeners such as e.g. Acetophenone derivatives or benzil ketals can be significantly increased in their photoreactivity if certain ferrocenium salts are added, although these salts are largely ineffective on their own for radical polymerizations.
  • Such combined systems therefore represent a significant improvement in curing, as can be measured as increased photosensitivity. This applies to a wide variety of materials, such as those used for image recording or other applications in which a higher sensitivity to visible light is desired. It should also be noted that this surprising improvement in radical photopolymerization is achieved without the addition of oxidizing agents.
  • R 1 as ⁇ -arene can be a mononuclear or multinuclear arene.
  • a multinuclear arene can be condensed or uncondensed, and the nuclei can also be linked via heteroatoms.
  • R 1 is preferably benzene or one or more of the substituents halogen, C 1 -C 12 alkyl, C 2 -Ci 2 alkenyl, C 2 -C 12 alkynyl, C 1 -C 8 alkoxy, phenoxy, cyano, C 1 -C 8 alkylthio, C 2 -C 6 alkoxycarbonyl, phenyl, C 2 -C 5 alkanoyl or benzoyl substituted benzene or unsubstituted or substituted by halogen or C 1 -C 12 alkyl or naphthalene or tetrahydronaphthalene.
  • R 2 as a substituted cyclopentadienyl anion can be mono- or poly-substituted and the substituents can be, for example, C 1 -C 8 alkyl, C 2 -C 6 alkoxycarbonyl, cyano, C 2 -C 5 alkanoyl or benzoyl.
  • alkyl, alkoxy, alkylthio, alkoxycarbonyl and alkanoyl substituents can be unbranched or branched.
  • substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl; Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-hexyloxy, n-octyloxy; Methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, n-pentylthio, n-hexylthio; Methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxy
  • alkyl, alkoxy, alkylthio and alkoxycarbonyl groups mentioned above preferably have 1-4, in particular 1 or 2, carbon atoms in the alkyl part and the alkanoyl groups mentioned above preferably have 2 or 3 carbon atoms.
  • R 1 is a substituted benzene, it preferably contains one or two of the substituents mentioned, in particular the substituents chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, cyano, methoxycarbonyl, ethoxycarbonyl or acetyl.
  • Suitable ⁇ -arenes as R 1 are benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, anisole, phenetol, dimethoxybenzene, p-chlorotoluene, chlorobenzene, bromobenzene, dichlorobenzene, acetophenone, trimethoxybenzene, dihydronaphaphthalene, diphenylthene, tetrahedral Biphenyl or dodecylbenzene.
  • R 1 is preferably benzene, toluene, xylene, cumene, mesitylene, chlorobenzene, chlorotoluene, anisole, dimethoxybenzene, biphenyl, diphenyl ether, dodecylbenzene, methylnaphthalene or tetrahydronaphthalene.
  • R 2 is preferably an unsubstituted or substituted by C 1 -C 4 -alkyl cyclopentadienyl anion, in particular the cyclopentadienyl or methylcyclopentadienyl anion.
  • a is preferably 1.
  • L are the elements Fe, Sn, Br, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn or Cu, but in particular B, P, As and Sb.
  • L is particularly preferably phosphorus.
  • Q as halogen is preferably chlorine, but especially fluorine.
  • q is preferably 1, m is preferably 4 or 6, Q is preferably fluorine and L is preferably B, P, As or Sb.
  • Examples of complex anions [LQ m ] -q are BF 4 - , PF 6 - , AsF 6 - , SbF 6 - , FeCl 4 - , SnCl 6 2- , SbCl6 or BiCl 6 - .
  • the anions BF 4 - , PF 6 - , AsF 6 - and SbF 6 - are preferred.
  • the compounds of the formula I are known compounds or can be prepared analogously to the known compounds.
  • the a-splitter type photoinitiators act on photoexcitation, i.e. upon absorption of actinic radiation, with the formation of an excited singlet state, which presumably forms a chemically reactive excited triplet state through intermolecular interaction.
  • the homolytic C-C cleavage of aromatic carbonyl compounds may be mentioned as an example, whereby the excited triplet state can lead to decomposition into a benzoyl radical and an alkyl radical.
  • This photolytic a-cleavage is widely known in the literature and is often referred to as Norrish I-cleavage.
  • the photoinitiators that act according to this mechanism primarily include carbonyl compounds, such as Aroyl ketals, benzoin derivatives, derivatives of a-hydroxy and a-aminoacetophenone, esters of an arylglyoxylic acid or acylphosphine oxides, but also compounds that do not contain carbonyl groups, e.g. aromatic halonium and sulfonium salts.
  • carbonyl compounds such as Aroyl ketals, benzoin derivatives, derivatives of a-hydroxy and a-aminoacetophenone, esters of an arylglyoxylic acid or acylphosphine oxides, but also compounds that do not contain carbonyl groups, e.g. aromatic halonium and sulfonium salts.
  • the sum of components (b) and (c) is generally 0.05 to 10% by weight of (a), preferably 0.2 to 5% by weight, in particular approximately 2% by weight.
  • the weight ratio of (b) is 6: 1 to 1: 4, a ratio of 2: 1 to 1: 2 is preferred.
  • Component (a) can consist of one or more polymerizable compounds.
  • Suitable free-radically polymerizable materials are in particular mono- or poly-ethylenically unsaturated compounds.
  • examples include: styrene, vinyl pyridine, vinyl acetate, divinylbenzene, vinyl ether, acrylamide, methacrylamide, methylene-bisacrylamide, unsaturated polyesters, especially those based on maleic acid, and also acrylic acid derivatives.
  • Preferred materials are the esters and amides of acrylic and methacrylic acid.
  • the esters can be derived from monovalent or polyvalent hydroxyl compounds.
  • monovalent hydroxyl compounds are methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, ethylhexanol, cyclohexanol, phenol or glycidol.
  • polyols are linear or branched alkane diols, such as, for example, ethylene glycol, propylene glycol, butanediol, hexanediol or octanediol.
  • polyols are diethylene glycol, triethylene glycol, polyethylene glycols with a molecular weight of 200 to 500, 1,4-dihydroxycyclohexane, 1,4-di (hydroxymethyl) cyclohexane, hydroquinone, resorcinol, 4- (hydroxymethyl) phenol, glycerol, 1,2 , 4-trihydroxybutane, trimethylolpropane, pentaerythritol, dipentaerythritol or low molecular weight polyester with terminal hydroxyl groups.
  • Further polyols are epoxy resin prepolymers containing hydroxyl groups or polyurethane prepolymers.
  • Preferred radically polymerizable materials are the acrylates and methacrylates of polyols, of epoxy resin prepolymers and of hydroxyl-containing polyurethanes.
  • Cationically polymerizable materials can also be admixed with the radically polymerizable materials, e.g. Epoxies, melamine resins or vinyl ethers.
  • the initiator system according to the invention can also initiate cationic polymerizations, radical and cationic curing take place side by side or in succession.
  • component (a) is liquid, components (b) and (c) can be dissolved in (a), possibly with gentle heating, and homogeneous liquid mixtures are obtained. If component (a) is solid, it can be dissolved in a suitable solvent or it can be melted to dissolve (b) and (c) therein. Of course, one can also dissolve (b) and (c) in a suitable solvent and mix these solutions with the liquid (a). All of these mixing operations are expediently carried out under red or yellow light.
  • the mixtures according to the invention are stable at room temperature in the dark or under yellow light and are therefore storable. When heated, the mixtures can harden, especially at temperatures near the decomposition point of (b) and (c).
  • (c) at least one photoinitiator of the a-splitter type, the sum of (b) and (c) being 0.05 to 10% by weight of the free-radically polymerizable material and the weight ratio (b) to (c) 6: 1 to 1: 4.
  • compositions to be cured are irradiated with electron beams or with actinic light, preferably with light of the wavelength 200-600 nm.
  • Radiation sources which are customary for this are e.g. Xenon lamps, argon lamps, tungsten lamps, carbon arc lamps, metal halide lamps and metal arc lamps, such as e.g. Mercury, low pressure, medium pressure or high pressure lamps. Metal halide lamps or high-pressure mercury lamps are preferably used. Irradiation with sunlight or fluorescent lamps is also possible.
  • the irradiation time depends on various factors, e.g. on the type of material to be hardened, on the type of radiation source and its power and its distance from the material. Today's radiation systems have outputs of 150 to 5000 watts. With such lamps, irradiation times of 10 to 60 seconds are usually sufficient.
  • the exposed materials can be post-treated thermally in order to achieve greater crosslinking of the polymer. This can e.g. done in conventional convection ovens or by infrared radiation or microwave heating.
  • compositions according to the invention can also contain other additives as are customary in the technology of photopolymerizable materials.
  • additives include pigments, dyes, fillers, reinforcing agents, flame retardants, antistatic agents, flow control agents, antioxidants or light stabilizers.
  • weak organic bases can be added, e.g. Nitriles, amides, lactams or urea derivatives.
  • small amounts of UV absorbers and / or organic dyes can be added.
  • compositions according to the invention can be applied to the substrates by customary methods.
  • Suitable substrates are e.g. Metals, silicon wafers, ceramic materials, glass, plastics, paper or wood. After hardening, the applied material forms a protective and passivating layer on the substrate.
  • the unexposed areas can then be removed with a suitable solvent.
  • a suitable solvent In the case of a liquid photopolymer, the unexposed parts can be blown away with hot air.
  • the relief image obtained in this way can be post-cured by further exposure or by heat treatment.
  • the coated material can also be used as a photographic recording material and can e.g. for the production of printing plates and printed circuits or as solder resist, photoresist or etching resist.
  • the use for the production of photographic relief images is also the subject of the invention.
  • the photoinitiator mixtures according to the invention increase the photosensitivity of such imaging systems without the amount of photoinitiator having to be increased, which is important for such applications is significant advantage.
  • the UV rays penetrate deeper into the layer, which results in better curing and thus higher optical resolution.
  • the mixture of the photopolymer and the two photoinitiators is applied in a layer thickness of approximately 1 mm to a black-painted aluminum sheet.
  • a first exposure is then carried out with the purpose of increasing the viscosity and thus reducing the oxygen content, which increases the sensitivity of the photopolymer.
  • this pre-exposure is usually done with a low-pressure mercury lamp, for example a so-called black light emitter.
  • the photonegative which is fixed on a glass plate, is brought up to a distance of about 0.5 mm from the photopolymer.
  • the main exposure then takes place, for example with a xenon lamp, for about 35-55 seconds. During this exposure, the photopolymer has hardened in the deeper layers in the exposed areas.
  • Example 1 The amounts of photoinitiators given in the table are dissolved in various free-radically polymerizable materials and the solution is applied in a thickness of 1.25 mm to non-reflective black paper. A step wedge with 50 steps of different optical permeability is mounted at a distance of 0.5 mm above the coating. The samples are exposed through this negative with a stationary mercury lamp, whereby an energy of 160 mJ / cm 2 is emitted. Then you determine the highest step of the step wedge under which a skin of the polymer has just formed. This number of steps is a good criterion for the relative sensitivity (photosensitivity) of the formulation. The higher the number of steps, the more sensitive the formulation. These results show the increase in sensitivity when combining both photoinitiators. The high photosensitivity of the samples is also evident in the premature gel formation when stored in brown bottles.
  • Example 2 A methacrylate-modified polyurethane with the photoinitiators given in the table is applied to a non-reflective black paper in a layer thickness of 1.25 mm. A 50 step wedge applied to a glass plate is mounted at a distance of 0.4 mm above the coating. The samples are exposed to an energy amount of 160 mJ / cm 2 using a 5 kW high-pressure mercury lamp. As described in Example 1, the highest level at which a skin of the polymer has just formed is determined and serves as a measure of the photosensitivity. The results are shown in Table 2.
  • Example 3 In this example the production of printing plates is simulated. An aliphatic polyurethane methacrylate is used as the photopolymerizable material, to which various amounts of photoinitiators A and B are added.
  • the photopolymer is only briefly pre-exposed with a xenon arc lamp without a mask.
  • the main exposure takes place through a negative film (from Gammatrol), which in addition to a line pattern has a semicircular scale of halftone dot grids with 27 gradations.
  • Level 27 has the largest screen dots, level 1 the smallest, corresponding to the finest screen on the printing plate.
  • Screen level 15-20 represents the gray tones on the print image. The finest screen is measured, which is still shown on the printing plate.
  • the fine halftone dots disappear when their shape is not fully developed and e.g. has rounded shoulders. Or the grid points have a mushroom shape and disappear during development.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
EP86810416A 1985-09-23 1986-09-17 Système de photo-initiation pour compositions polymérisables par vote radicalaire Expired EP0221010B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86810416T ATE42644T1 (de) 1985-09-23 1986-09-17 Photoinitiatorsysteme fuer radikalisch polymerisierbare materialien.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/779,343 US4707432A (en) 1985-09-23 1985-09-23 Ferrocenium/alpha-cleavage photoinitiator systems for free radical polymerizable compositions
US779343 1985-09-23

Publications (2)

Publication Number Publication Date
EP0221010A1 true EP0221010A1 (fr) 1987-05-06
EP0221010B1 EP0221010B1 (fr) 1989-04-26

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86810416A Expired EP0221010B1 (fr) 1985-09-23 1986-09-17 Système de photo-initiation pour compositions polymérisables par vote radicalaire

Country Status (12)

Country Link
US (1) US4707432A (fr)
EP (1) EP0221010B1 (fr)
JP (1) JPH0695212B2 (fr)
KR (1) KR900005848B1 (fr)
AT (1) ATE42644T1 (fr)
AU (1) AU588627B2 (fr)
BR (1) BR8604523A (fr)
CA (1) CA1262200A (fr)
DE (1) DE3663093D1 (fr)
ES (1) ES2000400A6 (fr)
SU (1) SU1560070A3 (fr)
ZA (1) ZA867185B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988002879A1 (fr) * 1986-10-14 1988-04-21 Loctite Corporation COMPOSITIONS A RADICAL LIBRE POLYMERISABLES A LA LUMIERE VISIBLE ET CONTENANT DES COMPLEXES METALLIQUES pi-ARENE
EP0320237A2 (fr) * 1987-12-08 1989-06-14 Mitsui Petrochemical Industries, Ltd. Composition durcissable par des rayons actiniques et milieu pour l'enregistrement optique contenant le produit durci de cette composition
EP1079276A1 (fr) * 1999-08-27 2001-02-28 AGFA-GEVAERT naamloze vennootschap Mélange photopolymérisable et matériau d'enregistrement fabriqué à partir de celui-ci

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Publication number Priority date Publication date Assignee Title
KR910000199B1 (ko) * 1986-04-15 1991-01-23 시바-가이기 코오포레이숀 액체 광개시제 혼합물
US4808638A (en) * 1986-10-14 1989-02-28 Loctite Corporation Thiolene compositions on based bicyclic 'ene compounds
DE3879278D1 (fr) * 1987-06-05 1993-04-22 Ciba-Geigy Ag, Basel, Ch
DE3888400D1 (de) * 1987-06-12 1994-04-21 Ciba Geigy Photoresistzusammensetzungen.
US4801392A (en) * 1987-07-02 1989-01-31 The Mead Corporation Magnetic recording compositions containing ionic dye compounds as initiators
JPS6454440A (en) * 1987-08-24 1989-03-01 Toyo Boseki Photopolymerizable composition
US4950696A (en) * 1987-08-28 1990-08-21 Minnesota Mining And Manufacturing Company Energy-induced dual curable compositions
US5147900A (en) * 1987-08-28 1992-09-15 Minnesosta Mining And Manufacturing Company Energy-induced dual curable compositions
US5086086A (en) * 1987-08-28 1992-02-04 Minnesota Mining And Manufacturing Company Energy-induced curable compositions
US4952612A (en) * 1987-08-28 1990-08-28 Minnesota Mining And Manufacturing Company Energy-induced curable compositions
JP2658123B2 (ja) * 1988-02-08 1997-09-30 東レ株式会社 感光性平版印刷版原版
US4985340A (en) * 1988-06-01 1991-01-15 Minnesota Mining And Manufacturing Company Energy curable compositions: two component curing agents
JP2757375B2 (ja) * 1988-06-02 1998-05-25 東洋紡績株式会社 光重合性組成物
DE3918105A1 (de) * 1988-06-02 1989-12-14 Toyo Boseki Photopolymerisierbare zusammensetzung
JPH022562A (ja) * 1988-06-13 1990-01-08 Toyobo Co Ltd 光重合性組成物
JPH021859A (ja) * 1988-06-13 1990-01-08 Toyobo Co Ltd 感光性樹脂組成物
JP3035740B2 (ja) * 1988-06-22 2000-04-24 東洋紡績株式会社 感光性樹脂組成物
DE3832032A1 (de) * 1988-09-21 1990-03-22 Hoechst Ag Photopolymerisierbares gemisch und daraus hergestelltes aufzeichnungsmaterial
US5102775A (en) * 1988-09-30 1992-04-07 Kansai Paint Co., Ltd. Visible light sensitive electrodeposition coating composition and image-forming method using the same
JPH02114266A (ja) * 1988-10-24 1990-04-26 Toyobo Co Ltd 光重合性組成物
US4954414A (en) * 1988-11-08 1990-09-04 The Mead Corporation Photosensitive composition containing a transition metal coordination complex cation and a borate anion and photosensitive materials employing the same
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EP1079276A1 (fr) * 1999-08-27 2001-02-28 AGFA-GEVAERT naamloze vennootschap Mélange photopolymérisable et matériau d'enregistrement fabriqué à partir de celui-ci
US6844136B1 (en) 1999-08-27 2005-01-18 Agfa-Gevaert Photopolymerizable mixture and recording material prepared therewith

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JPS6290648A (ja) 1987-04-25
SU1560070A3 (ru) 1990-04-23
BR8604523A (pt) 1987-05-19
AU588627B2 (en) 1989-09-21
EP0221010B1 (fr) 1989-04-26
CA1262200A (fr) 1989-10-03
ES2000400A6 (es) 1988-02-16
KR870003402A (ko) 1987-04-17
AU6308386A (en) 1987-03-26
US4707432A (en) 1987-11-17
JPH0695212B2 (ja) 1994-11-24
ATE42644T1 (de) 1989-05-15
KR900005848B1 (ko) 1990-08-13
ZA867185B (en) 1987-05-27
DE3663093D1 (en) 1989-06-01

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